CN109675564B - Preparation method and application of water hyacinth iron biochar - Google Patents
Preparation method and application of water hyacinth iron biochar Download PDFInfo
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- CN109675564B CN109675564B CN201910044653.2A CN201910044653A CN109675564B CN 109675564 B CN109675564 B CN 109675564B CN 201910044653 A CN201910044653 A CN 201910044653A CN 109675564 B CN109675564 B CN 109675564B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 240000003826 Eichhornia crassipes Species 0.000 title abstract 2
- 241000169203 Eichhornia Species 0.000 claims abstract description 33
- 241000196324 Embryophyta Species 0.000 claims abstract description 13
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 13
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910017626 NH4Fe(SO4)2 Inorganic materials 0.000 claims description 4
- 238000012258 culturing Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
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- 238000003756 stirring Methods 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052603 melanterite Inorganic materials 0.000 claims description 2
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- 238000000643 oven drying Methods 0.000 claims 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000005381 potential energy Methods 0.000 abstract description 3
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- 239000002994 raw material Substances 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 238000002441 X-ray diffraction Methods 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 3
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- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
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- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
- 229910018089 Al Ka Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a preparation method and application of water hyacinth iron biochar, which takes water hyacinth as a raw material and adopts an in-situ iron enrichment method to obtain 4-64 mg.L through plant solution culture for one month‑1The water hyacinth rich in iron is subjected to slow pyrolysis at the temperature of 500-900 ℃ and in the nitrogen atmosphere to prepare a series of water hyacinth biochar loaded with different concentrations, and the result shows that the water hyacinth biochar has a rough surface and a blocky structure, and the iron in the biochar is Fe2O3And Fe3O4Two oxide forms exist. By utilizing glassy carbon rotating disk electrodes modified by various biological carbon particles, H in neutral medium is explored through cyclic voltammetry2O2Electrocatalytic reduction reaction on different biochar catalysts shows that the common water hyacinths iron biochar sample has the maximum reduction current value for H2O2The electrocatalytic performance of the catalyst is the most excellent, and experiments of different sweep rates also prove that the catalyst also has potential energy storage properties.
Description
Technical Field
The invention relates to a preparation method and application of water hyacinth Fe biochar, and belongs to the field of environmental biology.
Background
Biochar is a high-specific-surface-area carbon-rich solid prepared by a thermochemical treatment method, has become a popular direction for research of researchers, and has been applied to a plurality of environmental fields such as soil remediation, pollutant adsorption and environmental management.
Hydrogen peroxide (H)2O2) Is an important chemical substance, plays an important role in a plurality of fields such as bleaching, disinfection, oral care, food safety and the like, and more importantly, as an intermediate product of human metabolism, excessive hydrogen peroxide can greatly reduce the oxidation resistance of the body, thereby inducing a series of diseases. Electrocatalytic reduction of H2O2There has been a long history of research, and the catalysts used often include single metals, metal complexes, metal organic heterocyclic compounds, etc., and NaBH was studied in the early Choudhury stage4/H2O2The electro-catalytic reduction of hydrogen peroxide by the Pt system obtains larger peak workSpecific density, but the Pt-based catalyst electrode has the same H2O2Disadvantage of self-decomposition, in order to reduce electrocatalytic reduction of H2O2In process H2O2The subject group of the Chinese Dalian connection substance uses Pd-Ag as a composite catalyst, and develops the self-decomposition reaction of H2O2The research of electrocatalytic reduction shows that the electrocatalytic activity of the composite catalyst is obviously enhanced, and the H is greatly reduced2O2A tendency to decompose into water and oxygen. The iron-biochar shows good catalytic performance in the applications of preparing liquid hydrocarbon from the biological synthesis gas, decomposing tar, bioremediation of waste water and the like. At present, the iron-biochar composite material is loaded with iron by methods of soaking biochar in an iron solution or directly mechanically mixing the biochar with iron oxide, and the like, and no report of preparing the iron biochar by adopting a plant enrichment way exists.
Disclosure of Invention
The technical scheme of the invention is that water hyacinth is subjected to in-situ enrichment of iron with different concentrations, then prepared into different biochar samples in a high-temperature pyrolysis mode, and applied to electrocatalytic reduction of H2O2Meanwhile, the electrochemical property of the stored energy is researched, so that H is reduced2O2And the purpose of energy storage. The specific method comprises the following steps:
the preparation method of the water hyacinth Fe biochar comprises the following steps:
(1) plant screening and cultivation
Screening healthy and strong water hyacinth, cleaning, putting into distilled water and Hoagland's nutrient solution for self-cleaning for 1 week, watering by using iron-containing solution, changing culture solution every week, culturing for 1-2 months, and adding deionized water for comparison;
(2) preparation of water hyacinth-ferrum biochar
Cutting the roots of the plants added with the iron element and the roots of the blank control group of deionized water, drying until no moisture exists, pumping air in a crucible under a closed condition, introducing nitrogen to balance the pressure inside and outside a pipe, adjusting the nitrogen flow rate to 10-20mL/min (the preferable scheme is that introducing nitrogen to balance the pressure inside and outside the pipe, and adjusting the nitrogen flow rate to 15mL/min) and sintering to obtain biochar; the sintering temperature rise rate in the sintering process is 15-26 ℃/min, and the temperature is kept for 0.5-2h after the sintering is carried out to the temperature of 500-900 ℃ (the preferable scheme is that the temperature rise rate is 23 ℃/min, and the temperature is kept for 2h after the sintering is carried out to the temperature of 700 ℃).
(3) Ash removal treatment of biochar
Grinding the biochar, pouring 3-6mol/L NaOH solution, stirring at 60-70 ℃ for 1-3h, filtering, washing with water, standing, pouring floating slag, and drying to obtain the water hyacinth Fe biochar.
The iron-containing solution comprises NH4Fe(SO4)2·12H2O or FeSO4·7H2O solution, said NH4Fe(SO4)2·12H2O or FeSO4·7H2The irrigation concentration of the O solution is 0.004-0.064 g/L.
The invention applies the prepared water hyacinth Fe biochar to electrocatalytic reduction of hydrogen peroxide under the condition of neutral medium.
The technical scheme of the invention adopts a method combining simple and easy-to-operate in-situ enrichment and high-temperature calcination to prepare and synthesize the iron composite catalyst taking the water hyacinth biochar as the substrate, and the following conclusion is obtained:
(1) a series of characteristic technical means such as SEM, XRD, XPS, AAS and the like prove that the enrichment mechanism of plants on iron with different concentrations is different, so that gamma-Fe is generated2O3And Fe3O4 two iron oxides.
(2) Modified electrode pairs prepared from 8-Fe-BC biochar samples in neutral medium to H2O2Has better catalytic effect and larger response current density of active substances, and is more beneficial to H2O2The research of different sweep rates shows the potential energy storage electrochemical performance of the catalyst.
(3) The cheap and easily obtained water hyacinth biomass which causes damage to the water body environment is used as a raw material to prepare the iron-loaded biochar electrode, and the method has good practical application value of using waste.
Drawings
FIG. 1 is a graph showing the growth change of plants in iron solutions of different concentrations, wherein the left graph shows the change of the plants on day 1, and the right graph shows the change of the plants on day 30.
FIG. 2 is an SEM image of a sample of biochar and an elemental EDS image of sample number 8-Fe-BC.
Fig. 3 is an XRD pattern of the biochar sample.
FIG. 4 is an XPS plot of Fe 2p for a biochar sample.
FIG. 5 is a cyclic voltammogram at different rotational speeds.
Fig. 6 is a graph of the geometric current activity of a biochar sample.
FIG. 7 is a cyclic voltammogram of sample 8-Fe-BC at different scan rates of 50mV/s to 200 mV/s.
Detailed Description
The experimental instrument used in the technical scheme of the invention comprises the following components:
scanning Electron Microscope (SEM) (Jeol, japan); x-ray diffractometer (XRD, D/max2500, Rigaku, Japan); ESCALB 220i-XL type photoelectron spectrometer (VG, UK); a tubular resistance furnace (model SK2, manufactured by Jian Li electric furnace Co., Ltd. in Yingshan county, Hubei); delta320pH meter (Mettler-Toledo, Shanghai, Inc.); a Pinnacle 900T Perkin Elmer type atomic absorption spectrometer; electrochemical tests all used the AUTOLAB (PGSTAT12) electrochemical workstation.
The experimental reagent used in the technical scheme of the invention comprises the following components:
ammonium ferric sulfate (NH)4Fe(SO4)2·12H2O, AR), sodium hydroxide (NaOH, AR), nitric acid (HNO)3，GR)，H2O2(the mass fraction is 30%), other reagents are analytically pure, and experimental water is Reverse Osmosis (RO) water and ultra-pure (UP) water.
Example 1
Plant cultivation
Selecting fresh water hyacinth which is robust in growth and has the same plant size in the same area of the Yangxi river of the university of the three gorges, cleaning the fresh water hyacinth by using tap water, self-cleaning the fresh water hyacinth by using distilled water and Hoagland's nutrient solution for 1 week, then carrying out irrigation culture by using iron-containing solutions with different concentrations, replacing the culture solution every week, setting a group of blank controls and six experimental groups for comparison convenience, marking different water hyacinth samples as 0-Fe-BC, 4-Fe-BC, 8-Fe-BC, 16-Fe-BC, 32-Fe-BC and 64-Fe-BC respectively, transplanting four water hyacinth plants in each pot, culturing the blank controls by using clear water, irrigating the experimental groups by using iron-containing solutions with different concentration gradients, setting the solutions with different concentration gradients required by the experiment as shown in Table 1, and culturing for 1 month, plant growth change was recorded as shown in figure 1.
The iron-containing solution is ammonium ferric sulfate [ NH ]4Fe(SO4)2·12H2O, 8.634g of ferric ammonium sulfate [ NH ] were weighed4Fe(SO4)2·12H2Dissolving O ] solid particles in water, transferring into a volumetric flask of 1000mL after completely dissolving, diluting to scale, mixing well, and making into iron standard stock solution with mass concentration of 1 mg. mL-1。
TABLE 1 setup of different concentration gradient iron solutions
After one month, finishing the cultivation of the water hyacinth enriching iron with different concentrations, firstly washing the plants with tap water once, then washing with distilled water for a plurality of times, cutting the roots, stems and leaves of the water hyacinth into pieces, classifying, and respectively drying in a 65 ℃ oven for 12 hours, wherein the 64-Fe-BC is seriously withered in the initial stage of cultivation, the former five water hyacinth samples are used in the following experiments, and the dried water hyacinth samples are respectively filled in sealed bags for later use. Preparation of biochar samples
Placing a certain amount of dried blank group of water hyacinth roots into a crucible, moving to a position close to an electric heating resistor in a tubular muffle furnace, sealing a pipe orifice at one end, pumping off air in the pipe from the other pipe orifice by using a vacuum pump, introducing nitrogen gas until the pressure inside and outside the pipe is balanced, and repeating the operation for 2 times to ensure that the inside of the pipe is in a vacuum environment. The nitrogen flow rate is adjusted to 15mL/min-1Setting the operation parameters of the temperature controller at 23 ℃ min-1The temperature rises to 700 ℃ at the temperature rising rate, and the operation is finished after 2 hours of pyrolysis. And after the muffle furnace is cooled to room temperature, closing a nitrogen cylinder valve, and lightly taking out the crucible in the furnace. In the same way, the experimental groups were confirmedCracking under certain conditions to obtain crude biochar, and preparing 3mol/L-1NaOH solution, the prepared crude product biochar is filled into a 100mL beaker, and 3 mol.L of a certain volume is poured into the beaker-1And stirring the NaOH solution in a 65 ℃ water bath kettle for 2 hours, washing with distilled water, filtering with a filter membrane for several times until the pH value of the supernatant of the solution is close to neutral, removing large-particle scum, drying in a 60 ℃ oven for 1 hour, and grinding with agate to obtain different biochar samples.
Scanning Electron Microscope (SEM) and energy spectrum analyzer (EDS) detection
Dissolving 10mg of different biochar samples in 1.5mL of absolute ethanol respectively, performing ultrasonic treatment for 10min, observing the apparent morphology characteristics of the biochar samples by a scanning electron microscope (JSM-7500F, Jeol, Japan), and analyzing the composition of elements contained in the biochar samples by an energy spectrum analyzer.
Characterization by X-ray diffraction (XRD)
An appropriate amount of a biochar sample was placed on a slide glass and subjected to a tabletting treatment, and crystal phases of each component in the biochar sample were measured by an X-ray diffractometer XRD (D/max2500, Rigaku, Japan) using a copper target (Cu K α, λ ═ 1.54178nm) as a target material of an X-ray source for XRD, a working voltage: 40kV, current: 40mA, scanning range 2 theta: 5-90 °, scanning speed: 8 ℃ min-1Scanning step length: 0.02 degree.
X-ray photoelectron spectroscopy (XPS) test
Photoelectron spectra of five biochar samples were tested and analyzed by ESCLAB 220i-XL photoelectron spectrometer (X-ray target source is double anode Al Ka (energy 1486.6eV) and Mg Ka X-ray (energy 1253.6 eV); power is 200W).
Atomic Absorption Spectroscopy (AAS) measurement
Respectively weighing 10mg of biochar sample, placing the biochar sample in a polytetrafluoroethylene digestion tank, adding 5mL of nitric acid and 1mL of hydrofluoric acid into the biochar sample by using a 5mL pipette, placing the biochar sample in a digestion furnace for digestion at the temperature of 180 ℃ for 10 hours, placing the biochar sample on a graphite furnace after natural cooling, heating and steaming to remove mixed acid in the polytetrafluoroethylene digestion tank, and using 5% of HNO3The solution is fixed to 25mL, and the solution is processed in a fume hoodThe process is carried out. The atomic absorption test was performed on a Pinnacle 900T PerkinElmer type atomic absorption spectrometer using a multielement standard solution to prepare 0.5 mg.l-1、1mg·L-1、2mg·L-1、3mg·L-1、5mg·L-1、8mg·L-1、 10mg·L-1Fitting a standard curve of iron by a computer, sequentially measuring the iron content of the sample in the digestion solution by an acetylene flame method, and converting the measured result into the iron content (mg.g) in the biochar sample-1)。
Electrochemical Performance test
10mg of a biochar sample was dissolved in 1mL of an aqueous ethanol solution (V)H2O：VC2H5OH1: 4) in the middle, after 30min of ultrasonic treatment, 10L of ethanol dispersion of the biochar sample is transferred to a carrier Al2O3And naturally airing the glassy carbon electrode polished by the polishing powder at room temperature, then continuously dropwise adding 10L of 0.5% Nafion fixing solution by using a liquid-transferring gun, and drying to obtain the glassy carbon working electrode modified by the biochar sample. The cyclic voltammetry electrochemical test is carried out in a three-electrode system, a platinum (Pt) sheet electrode is an auxiliary electrode, a Saturated Calomel Electrode (SCE) is a reference electrode, a glassy carbon disc electrode is a working electrode, and electrolyte is 0.1M PBS solution and 4mM H2O2The pH value of the solution and the electrolyte is 7.4, the scanning potential interval is-400 mV to 600mV, the rotation speed is 0 to 1600 rpm/min, the number of scanning turns is 10 circles, and the scanning speed is 50 to 200 mV/s. High-purity nitrogen is introduced for 10min before the electrochemical experiment to remove oxygen dissolved in the electrolyte.
FIG. 2 is an SEM image of five biochar samples, with the 0-Fe-BC sample being an iron-not-enriched biochar sample and the other samples being enriched with different concentrations of iron, and it can be seen that these biochar samples are massive and have rough surfaces, which provide a large number of sites for iron loading. In addition, the different biochar samples can still keep the original blocky structure appearance of the water hyacinth root to a certain extent after pyrolysis. EDS mapping shows the existence of elements such as Fe, O, C, Ca and the like in an 8-Fe-BC sample.
The surface composition elements of different biochar samples are measured, the analysis result is shown in table 2, 0-Fe-BC does not contain iron, 4-Fe-BC does not detect iron, and the enrichment amount of the water hyacinth to the iron element is small under the culture condition of the concentration. The 8-Fe-BC, 16-Fe-BC and 32-Fe-BC biochar samples all detected the presence of iron, the 32-Fe-BC sample had the highest mass and atomic percent of iron element at the surface, 23.22% and 9.01%, respectively, but the mass percent of iron (9.55%) of 8-Fe-BC was higher than that of 16-Fe-BC (4.8%), which the applicant believes was due to the formation of two different forms of iron oxide, as further demonstrated by XRD and XPS.
TABLE 2 EDS analysis of biochar sample surfaces
FIG. 3 is an X-ray diffraction (XRD) pattern of various biochar samples, from which it can be seen that 8-Fe-BC samples have weak and broad γ -Fe at 35.630 ° 2 θ and (311) miller indices hkl2O3The diffraction peak of (2) appears, and it is known that gamma-Fe is present2O3The unit cell parameters of (a) 8.351, b 8.351, c 8.351, and z 10.667, which belong to the cubic system, correspond to PDF cards 39-1346. Furthermore, CaCO occurs at 2 θ equal to 23.143 °, a equal to 4.98, b equal to 4.498, c equal to 17.020, z equal to 2, and 2 θ equal to 29.405 °, and the crystal plane index hk is (104), a equal to b equal to c, a equal to β equal to pi/2, and γ equal to 2 pi, respectively3Not only, the 16-Fe-BC biochar sample showed Fe belonging to the cubic system at a position of 2 θ 44.762 °3O4Diffraction peaks, namely different enrichment mechanisms of the water hyacinth on iron with different concentrations, are finally induced to generate gamma-Fe respectively2O3(8-FeBC) with Fe3O4(16-Fe-BC). EDS characterization of the 32-Fe-BC sample shows that iron element exists on the surface of the sample, but the formation of diffraction peaks related to iron in the bulk phase of the biochar sample is not found in XRD test, which shows that the iron-enriched concentration is too high, and the iron oxide crystal phase is not easily formed under the same thermal cracking condition.
In order to further determine the valence state of the iron element and the combination form of the compounds of the iron element in different biochar samples, the valence state is determined byThe above samples were subjected to test analysis by X-ray photoelectron spectroscopy (XPS) technique. As can be seen from FIG. 4, 8-Fe-BC has two distinct characteristic peaks at the binding energies of 724.8eV and 711.0eV, which represent gamma-Fe2O3Fe 2p of1/2And Fe 2p3/2The corresponding peak position and another characteristic peak appear at the position of 718.8eV of binding energy, and according to the report of the literature, gamma-Fe2O3There appears a characteristic satellite peak, which appears together with Fe 2p3/2(ii) related; 16-Fe-BC samples for Fe3O4All consistent with characterization of XRD.
The total iron content of different biochar samples is measured by an atomic absorption method, the results are shown in Table 3, and the total iron content of the 0-Fe-BC sample is 4.385mg g-1The source of the iron is attributed to the iron element absorbed by the normal growth of plants. In other groups, the iron content of the biochar sample is increased firstly and then decreased gradually along with the increase of the concentration of the initial iron culture solution, wherein the iron content of the 8-Fe-BC sample is the highest, and the iron content value is 20.730 mg/g. This shows that the absorption of iron by the roots of water hyacinth gradually reaches the upper limit of the stress concentration with the increase of the iron solubility, and thus the concentration of iron is reduced. According to XRD and XPS results, the water hyacinth has different regulation and control mechanisms for different iron enrichment, so that different iron oxides are generated.
TABLE 3 biochar sample atomic absorption assay
Electrocatalytic reduction of H2O2Technical scheme of performance
For independent comparison of different biochar samples at different rotation speeds for H2O2Electrocatalytic reduction ability of (c), fig. 5 tests different biochar catalysts vs2O2Comparison of catalytic Capacity, it can be seen from the graph that the reduction current value generated by 8-Fe-BC is the largest and in the presence and absence compared to other samplesUnder the condition of rotating speed, the influence of the rotating speed on the reduction current is large, and in addition, when the rotating speed is 0rpm, different biochar samples are applied to H2O2The generated reduction current tends to increase firstly and then decrease along with the increase of the concentration of the loaded iron, when the rotating speed is gradually increased to 1600rpm, the generated reduction current tends to increase firstly and then decrease compared with 0rpm, but the reduction current value is slightly increased compared with the reduction current value without the rotating speed, because the mass transfer capacity of the rotating disc electrode is greatly improved by increasing the rotating speed, and errors caused by different electrode polarization conditions and uneven current density in a non-rotating state are reduced, so that the reduction current value of the reaction is increased.
The diameter of the glassy carbon electrode used in the invention is 5mm, and the geometric area of the glassy carbon electrode can be calculated to be 0.196cm by a circle area formula2Then the geometric current density is
Here, I is the current intensity and a is the electrode geometric area. In order to further characterize the catalytic performance of the biochar sample, fig. 6 respectively compares the geometric current densities of different biochar samples, the geometric current densities can be used as one means for characterizing the catalytic activity of the catalyst, and as is apparent from the geometric current density values on the ordinate of fig. 6, the response geometric current density of 8-Fe-BC is greater than other values, which indicates that the catalytic performance of the biochar sample is better than that of other samples.
Based on the above research, 8-Fe-BC sample is selected as the optimal catalyst, and the cyclic voltammogram at different scanning speeds of 50mV/s to 200mV/s is further researched, as shown in FIG. 7, the area enclosed by the cyclic voltammogram gradually increases along with the increase of the scanning speed, and the cyclic voltammogram can almost keep a rectangular shape, which indicates that the 8-Fe-BC sample has higher charge transfer capacity, and the 8-Fe-BC sample contains more gamma-Fe2O3There is a certain relation, and the potential energy storage electrochemistry can be explainedGood prospect of properties.
Claims (1)
1. The preparation method of the water hyacinth Fe biochar is characterized in that the water hyacinth Fe biochar contains gamma-Fe2O3The preparation method comprises the following steps:
(1) plant screening and cultivation
Screening healthy and strong water hyacinth, cleaning, putting into distilled water and Hoagland's nutrient solution for self-cleaning for 1 week, irrigating with iron-containing solution, changing culture solution every week, and culturing for 1 month, wherein the iron-containing solution is NH4Fe(SO4)2·12H2O or FeSO4·7H2O solution, said NH4Fe(SO4)2·12H2O or FeSO4·7H2The pouring concentration of the O solution is 8 mg/L;
(2) preparation of water hyacinth-ferrum biochar
1 month later, cutting root of plant containing herba Eichhorniae and ferrum element, oven drying to no moisture, placing in crucible, pumping air under sealed condition, introducing nitrogen gas until the pressure inside and outside the tube is balanced, adjusting nitrogen gas flow rate at 15mL/min at 23 deg.C/min-1The temperature is raised to 700 ℃ at the temperature raising rate, the operation is finished after 2 hours of pyrolysis, and the biochar is obtained by sintering;
(3) ash removal treatment of biochar
Grinding the biochar, pouring into 3mol/L NaOH solution, stirring at 65 ℃ for 2h, filtering, washing with water until the pH value of the supernatant of the solution is close to neutral, standing, pouring out scum, and drying to obtain the water hyacinth Fe biochar.
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